Rubber conversion products and method of making same



lPatented Apr. 5, 1932 UNITED STATES PATENT OFFICE HARRY L. FISHER, OFAKRON, OHIO, ASSIGNOB IO THE B. If. GOODRIOE COMPANY, 01'

- NEW YORK, N. Y A CORPORATION 01' NI'W YORK RUBBER CONVERSION PRODUCTSAND HE'I'EOD OI sum 1% Brewing.

This invention relates to rubber conversion products of a type formed bythe reaction thereon of isomerizing reagents for rubber and to methods"of producing such con- (gg version products.

lhe present invention is based on the discovery that certain compoundswhen admixed with rubber and a phenol and subjected to moderatelyelevated temperatures liberate in to the rubber-phenol mixtureisomerizing agents for rubber which react with the rubber to formisomeric conversion products of rubber. Substances which operate in thismanner fall into no present accepted group M or class, but may beconsidered to form an empiricalclass of substances having in common theabove indicated properties. Such an empirical class has been found toinclude chlorinated rubber, rubber hydrochloride,

2 rubber sulfur chloride, chlorinated rub ber hydrochloride, pinenehydrochloride,

diphenylamine hydrochloride, trichloraniline hydrochloride,m-nitraniline hydrochloride, mercuric chloride, 'stannic chloride,napthalene tetrachloride, triphenyl chlormethane, zinc'bromide, mercuricbromide, rubber dibromide, diphenylami'ne hydrobromide, cadmium sulfate,aluminum sulfate, mercuric sulfate, diphenylamine sulfate, anddiphenylamine tri'chloracetate. These compounds when heated in thereaction mixture probably liberate their corresponding acids, such ashydrochloric acid, hydrobromic acid, sulfuric acid or trichloraceticacid, all of rubber and any of the hereinabove indicated compounds inthe presence of a phenolmay be effected by dispersingthe latteringredients directly into rubber and thereafter subjecting the admixtureto heat at elevated temperatures for such time as may be necessary tocomplete the conversion reaction.

59 What part the phenol takes in the reaction which have been proven bytest to be isomer- Application filed December 28, 1926. Serial No.157,825.

with the above indicated reagents is not now definitely known, butnumerous experiments indicate that it acts somewhat as a catalyst withthe compounds hereinabove mentioned to form in the reaction mixtureisomerizing iagents which efiect the conversion of the ruber. .In orderto illustrate the recesses described hereinabove in greater etail, thefollowing examples are given below: 60

Example 1.--Mix into 100 parts by weight ofwrubber 20 parts by weightofphenol and 20 parts by weight of mercuric chloride, as by adding thephenol and the chloride to the rubber on the mill during masticationthere- 05 of. When the ingredients have been thor oughly admixed,subject the batch to heat as b placing it in an oven maintained at 134Cl and continue the heating for about twenty hours. When cooled, theresulting conversion product is found to be a strong, firm,thermoplastic material. This conversion product needs generally to beprepared or reworked to adapt it as a raw material for commercial use.Such reworking may consist of homogenizing the mass, as by comminution,by mastication or by solution in an organic solvent, and it is alsodesirable in many cases to wash'the product free of residual acid andother water-soluble impuriso ties. The above indicated procedure ofreworking the conversion product can be carried outwithout eflecting anydeep seated. change in the conversion product.

Ewample zit-Into 100 parts by weight of 5 rubber are admixed, as bydirect milling, 20 parts of rubber hvdrochloi'ide and 20 arts ofresorcinol. When the ingredients ve been thoroughly admixed the batch issubjected to heat, as by placing it in an oven maintained at 324 for 20hours. When cooled the resulting conversion product is found to bee.hard, firm, tough material.

Example (S -Take parts by weight of rubber and admix ..therew1th 10parts of cat- 05 echol and arts of diphenylamine'hydro chloride. thebatch has been thoroughly admixed, place in a suitable heater maintainedat 320 F. for about 20 hours,

more orldss, or until the conversion is com- 100 plete. A hard, toughmaterial is thereby produced. p

In general, a batch consisting of rubber 100 parts by weight, a phenolto parts 5 and any one of the compounds selected from the aboveempirical class, 20 to parts,

when treated as above described in the preceding examples will yieldconversion prodnets of the general type described therein. mSpecificallythe following proportions to 100 parts of rubber have given satisfactoryconversion products, the numeral indicating parts by weight: (a)chlorinated rubber 30,

resorcinol 20; (6) rubber sulfur chloride 30, 15 resorcinol 20; (c)pinene hydrochloride 30,

resorcinol 20; (d) trichloraniline hydrochloride 30, resorcinol 20; (e)mercuric chloride 20, catechol 20; (f) stannic chloride (crystalline)30, resorcinol 20; (g) naphthalene 20 tetrachloride 30, resorcinol 20;(h) triphenyl chlormethane 30, resorcinol 20; mercuric bromide 30,resorcinol 20; (7') rubber dibro- -mide 30, resorcinol 20; (7c)diphenylamine hydrobromide 25, resorcinol 20; (l) cadmium 26 sulfate(crystalline) 30, resorcinol 20; m) aluminum sulfate (crystalline) 30,resorclnol 20; (n) mercuric sulfate 30, resorcinol 20; (o) diphenylaminesulfate 20, resorcinol 20; (p) diphenylamine trichloracetate 30, resor-30. cinol 20.

Experiment has shown that the reagents above specified will in generalreact with rub her in solution, when subjected to steam bathtemperatures for from 1 to 3 days, but that larger proportions ofreagents are necessary to carry out the reaction, generally the phenoland the compound of the above noted empirical class must be used inquantities equaling the weight of the rubber and the reaction isfacilitat by using several times the weight of phenol. The followingexample is illustrative of this embodiment of my invention and is heregiven as a type, it being understood that the compounds of the empiricalclass above defined may in general be substituted therein in place ofthe mercuric chloride, specifically recited.

Emample 1;.Mix into 100 parts by weight of a 5 per cent solution ofrubber 20 parts by weight of phenol and 5 parts by weight of mercuricchloride, thoroughly admixing the ingredients. Place the admixture in asuitable receptacle, under'reflux, if desired, to prevent escape ofsolvent, and apply heat thereto, as on asteam bath. and continue the.

product is to be used insolution, the liquid reaction mixture may incertain cases be ditechol, the naphthols and p-chlorphenol.

The alternative procedures indicated in this paragraph need not bespecifically ,set forth herein since they are in all substantialrespects similar to the procedures described above. 1

Analysis of the purified conversion products prepared in any of the wayshereinabove described indicates that 5 these conversion products areisomers of rubber havin a chemically less unsaturation than rub er. Theyare generally tough, strong solid materials which are useful as rawmaterial in various industrial operations.

It is to be understood that the above examples are given merely by wayof illustration and that various modifications in the roportion of theingredients specified and in the time and temperature of carrying outthe conversion reaction may be employed by those skilled in this artwithout departing from the principles of this invention.

What I claim is:

1. The method of treating rubber which comprises admixing with rubber aphenol and a. substance selected from the empirical class consisting ofchlorinated rubber, rubber hydrochloride, rubber sulfur chloride,chlorinated rubber hydrochloride, pinene hydrochloride, diphenylaminehydrochloride, trichloraniline hydrochloride, m-nitranilinehydrochloride, mercuric chloride, stannic chloride, naphthalenetetrachloride, triphenyl chlor-methane, zinc bromide, mercuric bromide,rubber dibromide, diphenylamine hydrobromide, cadmium sulfate, aluminumsulfate, mercuric sulfate, diphenylamine sulfate, and diphenylaminetrichloracetate, and heating the mix.

2. The method of treating rubber which comprises admixing with rubber aphenol and a substance selected from the empirical class consisting ofchlorinated rubber, rubber hydrochloride, rubber sulfur chloride,chlorinated rubber hydrochloride. pinene hydrochloride. diphenylaminehydrochloride, trichloraniline hydrochloride, m-nitranilinehydrochloride, mercuric chloride, stannic chloride, naththalenetetrachloride, triphenyl chlor-methane. zinc bromide, mercuric bromide,rubber dibromide, diphenylamine hydrobromide, cadmium sulfate, aluminumsulfate, mercuric sulfate, diphenylamine sulfate. and diphenylaminetrichloracetate. heating the mix, and reworking the product forindustrial use.

3. The method of making conversion products of rubber which comprisesadmixing with rubber a phenol and a substance capable llll of liberatingin the rubber-phenol mix, un-

der the influence of heat, an isomerizin agent for rubber of the classconsisting of drochloric acid, hydrobromic acid, sulp urlc acid andtrichloracetic acid, and heating the mix.

A composition of matter comprising the product of the reaction, undertheinfluence oi heat, of rubber, a phenol and a substance capable ofliberating in the rubber-phenol min, under the influence of heat, anisomerizing agent for rubber of the class consisting of hydrochloricacid, hydrobromic acid, sulphnric acid and trichloracetic acid.

b; The method of treating rubber which comprises admixing with rubber aphenol and a substance selected from a class consisting ofhydrochlorides and hydrobromides of a weak organic base capable ofliberating a hydrogen halide in the mix at moderately elevatedtemperatures, and heating the mix.

b. The method of treating rubber which comprises admixing with rubber aphenol and a substance selected from the group consisting ofdiphenylamine hydrochloride, trichloraniline hydrochloride,m-nitraniline hydrochloride and diphenylamine hydrobromide, and heatinthe mix.

'l'. The metho of preparing conversion products which comprises treatingrubber with a phenol and with diphenylamine hydrochloride.

8. The method of treating rubber which com rises admixing with rubber aphenol and a su stance selected from the group consisti ng of diphenlamine hydrochloride, trichloraniline hydrochloride, m-nitranilinehydrochloride and diphenylamine hydrobro-' mide, and heating the mix andthereafter rewar-Eng the product for industrial use.

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9. A composition of matter comprising the firoduct of the reaction,under the influence of eat and in the presence of phenol, of rubber anda substance selected from a class consisting of hydrochlorides andhydrobromides of a weal: or anic base capable of liberating a hydrogenalide at moderatelyelevated temperatur'es.

W. A composition of matter comprising the-product of the reaction,under'the influence ofheat and in the presence of phenol, oi rubber anda substance selected from the group consisting of diphenylaminehydrochloride, trichloraniline hydrochloride, m"- nitraniline hdrochloride and diphenylamine hydrobromi e. a

Ill. The method of making conversion products of rubber which comprisesadm1xmg with rubber a phenol and a substance capable of liberating inthe rubber-phenol nnx under the influence of heat a strong nonoxidizingacid, and heating the l2. Acomposition of matter comprising the productof the reaction, under the inbuence of heat, of rubber, a phenol, and asubstance capable of liberating in the rubher-phenol mix under theinfluence of heat a I strong non-oxidizing acid.

In witness whereof I have hereunto set my hand this th da of November1926. RY L. rrsimn.

